EP2654449A1

EP2654449A1 - Method for fractionating jatropha seeds

Info

Publication number: EP2654449A1
Application number: EP11799685.0A
Authority: EP
Inventors: Stefan Kirchner; Detlef Ullmann; Ines SPEISER
Original assignee: GEA Mechanical Equipment GmbH
Current assignee: GEA Mechanical Equipment GmbH
Priority date: 2010-12-21
Filing date: 2011-12-16
Publication date: 2013-10-30
Anticipated expiration: 2031-12-16
Also published as: US20140057030A1; WO2012084730A1; ZA201304096B; AP3548A; MX2013007170A; AR084434A1; DK2654450T3; EP2654450B1; US20130345456A1; CN103369970A; CN103369970B; DE102011056557A1; WO2012084729A1; CN103379830B; MX344934B; AP3714A; CN103379830A; EP2654449B1; EP2654450A1; ES2594580T3

Abstract

The invention relates to a method for the solvent-free fractionation of shelled and comminuted jatropha seeds that have a phorbol ester content. At least the following fractions are obtained: a shred fraction, the phorbol ester content of which is reduced relative to the phorbol ester content of the jatropha seeds, and an oil that contains phorbol ester. The method has at least the following method steps: adding water and acid to the comminuted jatropha seeds, thereby forming a suspension that contains oil, the pH value of the suspension being set to <= 3.5; separating crude oil from the suspension that contains oil, preferably in the centrifugal field in order to form the crude oil fraction and the shred fraction; adding oil that is free of a phorbol ester content or at least has a reduced phorbol ester content, in particular vegetable oil, to the shred fraction; and separating extraction oil from the shred fraction from step 400), preferably in the centrifugal field.

Description

Process for fractionating jatropha seeds

The present invention relates to a method for fractionating jatropha seeds.

EP 0 267 933 A1 discloses a process for obtaining vegetable oil in which at least one reagent for reducing the phospholipid content to the oil-containing material is added. At this time, in preparatory steps, plants such as e.g. Soybeans or corn, cleaned, dried and shelled. Subsequently, these plant parts can be ground. In this case, for example, additional oil is added. In the extraction of vegetable oil from these soybeans or corn, i.a. also used hydrochloric acid. This serves to reduce the phospholipid content. In this case, a conversion of a hydrophobic phospholipid into a hydratable species occurs. However, since the hydration of phospholipids is reversible, chelating agents, precipitants or the like must also be used to stabilize the phospholipids in the aqueous solution.

GB 1 179 584 A discloses a process for the production of fats. The aqueous extraction of animal fats was optimized so that such a fat was extracted in a pH range between 4.1 to 5.8. This pH can i.a. by adding acids, e.g. Hydrochloric acid, sulfuric acid, citric acid or acetic acid can be achieved. WO 98/53698 A1 and EP 1 905309 A1 disclose processing of rapeseeds, soybeans, corn and sunflower seeds. These are ground first. Subsequently, solids are removed. Finally, a washing of the oil phase takes place, it being possible to adjust a pH between 2-10 by adding Tris-HCl during washing. This is followed by formulation into an emulsion. This emulsion is used in the food and feed sector, but also in combination with pharmaceutical and cosmetic products.

GB 1 402 769 A discloses a process for recovering oil by an enzymatic process. As a result of the enzymatic treatment, which takes place at pH values between pH = 3 and pH = 6, the decomposition of the cell walls of the oily vegetable product with release of the oil within 2 to 24 hours.

EP 2 163 159 A1 discloses a recovery of oil from a rapeseed. After pressing and peeling, the rapeseed is pressed

Rapeseed, which produces a press cake and rapeseed oil. The rapeseed oil is freed of phospholipids which agglomerate in a reaction tank in a process step called "degumming". This is followed by a process step of drying and esterification. By transesterification, a separation of biodiesel and crude glycerol takes place. In subsequent subsequent steps, proteins and various other valuable substances can be obtained from the different fractions of rapeseed oil or rapeseed cake. The method described here is only of limited suitability for the production of fuels, since the oil yield during the pressing of peeled rapeseed is very low. Due to the high residual fat content in the de-oiled press cake, this can only be recycled to a limited extent.

When using fuels from oil plants, especially the oil from the jatropha seeds, also called purging nuts, has proved to be an interesting alternative, since this jatropha oil has a higher cetane number compared to rapeseed oil and because the jatropha plant grows on nutrient-poor soils.

Today's methods primarily use a squeezing of the jatropha seeds. In order to achieve a high yield, a significant amount of shell in the product is imperative. The resulting by-products are returned as fertilizer to the Jatropha plantations, or pressed into pellets marketed as fuel. Since Jatropha owns a large proportion of high-quality proteins in addition to oil, attempts should be made to obtain the by-products obtained during the oil production in such a way that they can be marketed as high-quality feedstuffs.

A problem here is the relatively high proportion of woody constituents (indigestible) in the husk of the seed and in the high content of phorbol esters, which have a toxic effect on most animals. However, the method of pressing used today (eccentric screw press) requires the shell portion to squeeze the oil, the press cake thus contains all shell components. Thus, this product has a lower protein content and a high proportion of indigestible components, so in principle it is not or only partially usable as feed.

A possible detoxification, ie essentially the separation of phorbol esters from the press cake by means of methanol, is described in WO 2010/092143 A1. According to this teaching, phorbol ester is extracted by means of a technically quite complicated process, but without significantly changing the protein content of the product. By multiple extraction by means of methanol in a ratio of 1:10, the material is deprived of phorbol ester. In addition, the description of the introduction of WO 2010/092143 A1 describes further methods for reducing the phorbol ester content of a jatropha seed, the common problem of which, however, is the only conditional economic efficiency.

Thus, due to the properties of methanol (explosive, toxic, valuable), complete separation and recovery of large quantities of the solvent is a prerequisite for economical operation. This makes this method expensive, so that the economical use of this method is problematic. A classic hexane extraction can not be used to reduce the phorbol esters because they are not or only slightly soluble in hexane.

Here, the invention takes a different, more economical way, which is described in claims 1, 2 and 23.

Advantageous embodiments are specified in the subclaims.

In this way, apart from a crude oil as a fuel, other ingredients of the jatropha seed can be utilized very economically. The claims 1, 2 and 23 each relate to different variants in which advantageously different numbers Recycled material phases can be obtained from various preprocessed or unprocessed jatropha seeds.

The method described here differs significantly from the methods used today, since the main components allow bowls (40%), oil (35%), high-protein meal (25%) and phorbol esters to be recovered separately.

By separating phorbol esters, it is also possible to utilize the protein-rich meal as feed. In this way, a significantly improved added value can be achieved than with the conventional methods.

It will remove the shell parts of the Jatropha seeds, which may be up to 40% of the total weight. These may e.g. used for power generation of the plant, which may be particularly important in remote locations without power supply. Thus, the protein content in the de-oiled meal can be raised from approx. 18% to 55%.

Another requirement for the use of the protein-rich meal is the reduction of the phorbol ester content, so that the meal can be safely used as pet food.

The crude oil obtained here is an intermediate in the production of a fuel. It contains a proportion of residual water and possibly even smaller solid particles of the plant seed. The preferably used as a supplement oil polishing is a method for cleaning the oil. Here, the crude oil is further processed by means of filter technology or separation technology and cleaned or separated from solid residues and water. In this case, the solids content of the polished crude oil is reduced so that this oil can be used as fuel. By drying, the residual water content in the fuel is lowered to preferably 0.1% by weight or less.

The solid phase obtained in oil separation is an intermediate in the recovery of a high-protein meal. The oil obtained in this way is extremely low in phosphates, magnesium and calcium and, without further processing, complies with the standard for biofuels (DIN 51605). In contrast to press oils, a complex refining of oils can thus be avoided.

By adding oil which has no or only a very low phorbol ester content (sufficiently lower than in the scrap to be reduced in the phorbol ester content), phorbol esters remaining in the wet shot are transferred to the oil phase. By depositing the oil, the phorbol ester content in the meal is reduced to the point where it can be used as feed. The meal can preferably be used for pet food.

According to the invention, the fractionation of Jatrophasamen, ie the Purgiernüssen the Jatrophapflanze.

Preferred embodiments of the method are the subject of

Dependent claims.

Prerequisite for a separation of Phorbolestern and for obtaining protein-rich meal is first the effective separation of the oil. In the following, first of all, the pH value setting of the meal 200 is considered more closely.

Water and acid may be added separately to the suspension or may be mixed to a dilute acid prior to addition to the suspension, with the dilute acid already having an appropriate concentration prior to addition to adjust the pH of the suspension to 3.5 or to adjust less.

In extracting jatropha seed fuel having a fat content of more than 30% by weight, preferably more than 40% by weight, it has surprisingly been found that the yield of crude oil at a pH of less than 3, 5 increases significantly.

Although at a pH of <= 3.5, a significant increase in the yield of oil compared to a pH-neutral processing can be observed, a particularly advantageous increase in the yield can, however, in a suspension with a pH <= 3, 2 can be achieved. A further increase in the yield of oil can be achieved by adjusting the pH of the suspension is carried out specifically by hydrochloric acid.

The largest possible digestion of crude oil from the comminuted plant seeds or nuts can be achieved by a residence time of at least 30 minutes, preferably 30-60 minutes, after the addition of the acid. Since a higher temperature favors the digestion of the crude oil from the plant seeds or nuts, it is advantageous if a temperature of 60-80 ° C, preferably 80-95 ° C is set in the product with the added water. The plant seeds may be cleaned prior to crushing to remove foreign matter attached to the plants. In addition, the content of solids and foreign substances in the suspension can be reduced prior to crushing by peeling and drying in advance. Alternatively or additionally, the yield of fuel can be increased by crushing the plant seeds or nuts through a mill having a fine freeness. Due to the finer grind of plant seeds or nuts less crude oil is retained in the interior of the solids. Optionally, the separation of the crude oil by repeated de-oiling out of the suspension. The suspension is introduced after a first de-oiling with a crude oil content of 4 percent or less in a second decanter or recycled to the decanter of the first DEÖLUNG for a further de-oiling of the suspension.

By mixing the thus obtained aqueous solid phase with oil without Phorbo- lestern existing in the product phorbol esters can be extracted.

Subsequently, this oil is separated off with the dissolved phorbol esters in the decanter. The extractant may be foreign oil or, preferably, jatropha oil, previously separated from the phorbol esters by suitable procedures.

A washing of the crude oil to obtain the fuel can advantageously be carried out in a centrifuge, preferably a separator. Hereinafter, the invention with reference to an embodiment, the

Fractionation of Jatropha seeds, described in more detail with reference to the drawings. It shows:

1 shows a plant for obtaining a fuel from Jatropha seeds;

2 is a diagram illustrating the dependence of the oil content in the deoiled suspension at different pH values;

3 is a diagram illustrating the dependence of the oil content in the deoiled suspension of the acid used;

Fig. 4 is a diagram illustrating the dependence of the oil content in the deoiled suspension on the residence time; and

5 shows a flowchart for illustrating a preferred method sequence according to the invention.

Fig. 1 shows schematically a plant with which in a preferred embodiment Jatropha seeds A are processed to a Jatropharohöl D, which is suitable as a fuel, the Jatropha seeds or nuts were preferably previously cleaned and peeled.

In a first step of the processing, the jatropha seeds A are first transferred to a mill 1 for comminution. The purging nuts are broken up and crushed in a grinder. If necessary, this grinding process can be favored by supplying additional oil. The fragments of crushed jatropha seeds have a certain average grain size, which is determined by the grinder. This can be done for example in gap mills.

Even before crushing the Jatropha seeds are peeled and / or dried. These preparatory steps facilitate the comminution or milling of jatropha seeds. At the same time, the protein content is significantly increased by separating the shell components.

This can be seen as a decisive advantage over the methods used today, since now the shell fraction can be used separately, and the protein content of the de-oiled meal permits use as pet food. After grinding, the crushed jatropha seeds are transferred as an oil-solid mixture in a buffer tank 2. From there they are transported via a first eccentric screw pump 3 to a mixer or a mixing station 4.

In the mixing station 4, the ground product is supplied with hot water and acid, preferably HCl, and mixed so that the suspension has an elevated temperature of 60-80 ° C., preferably 80-95 ° C. In this particularly preferred introduction of hot water and acid, results in a suspension of solids, oil and water, which has a pH of <= 3.5.

To increase the yield of fuel and to obtain a low-oil meal, it is essential that the resulting suspension has a pH of <= 3.5.

The hot water and the acid, preferably concentrated hydrochloric acid, may also be introduced separately into the mixing station and form a suspension with a pH of <= 3.5 by intensive stirring.

While this sequence of operations is not preferred since a high concentration of acid is formed locally in the suspension, it may alternatively be used to add a dilute acid to form a suspension.

In a further, but also less preferred variant of the invention, to adjust the pH also another acid, e.g. Sulfuric acid or citric acid instead of hydrochloric acid.

Subsequently, the suspension is preferably transferred into a transfer container 5. It has surprisingly been found that the crude oil yield can be additionally increased advantageously within a residence time. The sedimentation is prevented by gentle stirring and thus improves the yield. For this purpose, the dwell 5 on a stirrer 6.

The residence time in the container 5 Verwe can be between preferably 30-60 minutes. Depending on the raw material and the acid used, the crude oil yield may even decrease slightly over a longer residence time. From the container Verwe over the suspension is transported via a second eccentric screw pump 7 to a decanter 8. This decanter can be designed as a two-phase separation decanter, the first phase consisting of deoiled suspension with a residual oil content of less than 6% by weight, based on the content of solids in the suspension, and the second phase consisting of vegetable crude oil and if necessary, dispersed dissolved solid particles and residual water.

As an alternative to a two-phase separation decanter, the de-oiling can also be carried out in a 3-phase decanter or in a combination of clear decanter and subsequent 3-phase separator.

The vegetable crude oil is collected in a container 9 and passed through a third eccentric screw pump 10 and via a heat exchanger 1 1, preferably a plate heat exchanger, to a centrifuge 12. Between the heat exchanger 1 1 and the centrifuge 12, a feed for hot water is arranged. This water advantageously has a temperature between 60-80 ° C, preferably 80-95 ° C, on.

The centrifuge 12 is preferably designed as a three-phase separator, wherein the separator is both a separation of the water and oil phase, as well as a clarification of the oil and water phases of solid particles.

A clear oil phase is thus removed from the centrifuge as jatropha oil, which can be further processed by neutralization and drying to form a product which is suitable for use as fuel in internal combustion engines.

Furthermore, the residual water content of the oil phase following the oil polishing can be reduced by vacuum drying, not shown here, to a residual water content of about 0.05% or less.

By neutralizing, the free fatty acid content can be reduced.

An important step in optimizing the extraction of oil from Jatropha seeds is to optimize the pH setting to <= 3.5. A further advantageous increase in the yield is achieved by the choice of a suitable acid, the residence time, the ratio of crude oil and water and / or acid in the suspension and the fine adjustment of the pH.

2 shows in a diagram measured values of the residual oil content in deoiled suspensions at different pH values, which were removed from a laboratory centrifuge 8. A lower residual oil content is significant for a better yield of jatropha oil and a higher protein content in the meal. A high residual oil content of the suspension thus reduces the yield of the recovered Jatrophaöls and reduces the protein content in the shot.

The temperature of the suspension was always 90 ° C, the residence times in the retention tank were always 60 min and the ratio of water to solid-oil mixture was always 1 + 1. The experiments pH = 3 were carried out with hydrochloric acid. In the suspension at pH = 5.5, citric acid was used to adjust the pH.

The different residual oil contents of the measured values shown in the diagram show no significant differences in the residual oil content at pH values between 5.5-6.5 to the residual oil content of an aqueous extraction in the pH-neutral range. At a pH of 3.0, however, a significant reduction of the residual oil content to 3.6% can be observed. As can be seen from the diagram, an increase in the yield of jatropha oil is surprisingly found when the pH is lowered to below 3.0.

In addition to the essential factor of the pH, the use of different acids leads to different yields of jatropha oil. In the diagram of FIG. 3, citric acid, hydrochloric acid and sulfuric acid in water were compared under comparable measuring conditions. The temperatures of the suspension were always 90 ° C, the pH of the solutions was always 3.0, the residence times in the second buffer tank always 60 min and the ratio of water to solid-oil mixture was always 1/1. It is evident from FIG. 3 that extraction with hot water with addition of hydrochloric acid over sulfuric acid and citric acid is preferred, since when a particularly high proportion of jatropha oil can be extracted from the solids of the suspension.

4 shows a tendency with regard to the residence times of the suspension in the container. These experiments were carried out with the addition of an aqueous citric acid solution at a pH of 3.0. It can be seen that a residence time of 30 minutes is sufficient to achieve the digestion of the oil phase from the suspension. Too long residence time (over 60 min) in the retention tank leads to an increase in the residual oil content and thus to a reduction in the overall yield. However, the dependence on the residence time is also at least partially dependent on the acid used. Thus, the residence time of 30-60 min has proven to be particularly advantageous when using HCl.

It has been found in experiments that an additional increase in the yield of fuel can be achieved, provided that the ratio of water to product after the addition of water and acid in step b) is in the range between 1/2 to 2/1.

Particularly preferably, the water content in the suspension is greater than 35% by weight, preferably greater than 40% by weight.

It has been found, in particular, that a ratio of 1 + 1 between the solid-oil mixture and the aqueous phase, ie a water content of about 50% in the suspension, is particularly advantageous.

In addition, a variant of the invention with reference to FIG. 5 will now be explained in more detail.

The subsequent numbering of the steps is easier to assign

First, the Jatropha seed is provided (step 10).

Then it is broken (step 20). Then the Jatropha seed is peeled (step 50). 35-40% (w / w) and thus the protein content of the husked Jatrophasamen already compared to the seed in a simple manner from about 16% (w / w) to about 25% (w / w). w) increased.

In addition to the increase in the protein content, about 16% of the phorbol esters with the shells are also removed during peeling and thus the amount of phorbol esters in the residual product is already reduced in a simple manner. In a next step 100, the Jatropha kernels will be finely ground. Experiments showed that a fineness with 50% of the particles smaller than 22 μιη (10% less than 4 m, 90% less than 280 μιη) caused optimal cell exclusion. Hereby, the plant cells are opened up so far that the oil escapes from the cells and is free.

Subsequently, the so-digested material is mixed with water and stirred carefully in a stirred tank. By reducing the pH to pH <3.2 by the addition of acid, it has surprisingly been found that the residual oil content was greatly reduced and thus the oil yield could be significantly increased (step 200). Different acids have a different influence on the residual oil content.

Thus, the residual oil content of 15.5% (w / w) could be reduced without pH shift to 8.5% with the addition of sulfuric acid. When using hydrochloric acid, the residual oil content was reduced to 3.5%

Experiments have shown that by maintaining the optimum residence time, the yield of oil can be significantly increased. The best results were obtained with a residence time of 60-90 minutes (step 250).

Then a first separation takes place in the centrifugal field, in particular a decanter in step 300): deposition of jatropha oil (jatropha crude oil) from the oil-containing suspension in the centrifugal field to form the jatropha oil fraction and the wet solid (scrap) fraction. Surprisingly, it has also been shown that the content of phorbol esters (PE) in both the oil phase and in the solid phases (shells and pellets) is so much lower than in the separation by means of screw presses (see Experiment 7 below). Since this substance is classified as highly toxic, the degradation of PE is to be estimated as an advantage compared to the currently used process.

In the aqueous process, the amount of phorbol ester in the meal is significantly reduced, for example by 92%, while the reduction in the press cake was lower, as surprisingly, for example, only 67%.

The remaining in the deoiled solid phorbol esters are still classified as toxic at a concentration of about 0.7 mg / g, so that further steps are necessary to further reduce the concentration. For this purpose, the deoiled solid (wet shot) is extracted with phorbol ester-free oil (steps 400, 500). These steps include adding vegetable oil (as part of step 400) and separating an oil phase from the wet and oiled shot in the centrifugal field at step 500. It is advantageous for the result if, in step 400, vegetable oil is in ratio between 1 + 10 to 1 + 1 - 1. Value: vegetable oil; 2: value residual oil content in shot fraction - is used.

It is conceivable to repeat steps 400 and 500 several times (3rd, 4th ... oil extraction).

The thus obtained moist flour or SchrotVFeststoffphase is sufficiently reduced in the phorbol ester content in order to use it as a valuable material.

A particular advantage of this process is that oil as extractant requires no special provisions with respect to explosion protection and complete recovery.

In a first experiment (experiment 8) a commercially available rapeseed oil was used instead of extracted Jatropha oil. 100 g of jatropha seed oil de-oiled in the above-described process was mixed with 10 g of rapeseed oil and spun in a laboratory centrifuge for 3 minutes at 4,500 g. The free oil was separated. The thus deoiled solid was dried and examined the phorbol ester content in the solid phase and in the oil phase. The phorbol ester content in the solid phase could be reduced from 0.68 mg / g to 0.38 mg / g. In the oil phase, the content of 0.00 mg / g (rapeseed oil addition) was increased to 2.65 mg / g in the mixed oil from the rapeseed oil and the residual oil in the shot. Thus it can be shown that phorbol ester can be extracted with vegetable oil. The overall oil obtained in the process described (jatropha oil, mixed oil) is surprisingly characterized, inter alia, by a very low phosphorus, calcium and magnesium content (experiment 6). The measured values were below the detection limit. Such low values can be achieved only conditionally with classical methods, and then by refining at considerable expense.

Since phorbol ester-free vegetable oil is not always available, Jatropha oil can also be used as an alternative, from which the phorbol esters have previously been separated. This is shown in Fig. 5 right.

In a first step, the phorbol ester oil from step 300 and, if appropriate, 500 with alcohol are extracted for this purpose (step 600). For this purpose, different alcohols can be used. Then an oil separation (step 700) preferably takes place in the centrifugal field. This alcohol extraction of the oil phase can be repeated one or more times (step 600 ', 700'). The alcohol is separated off with the phorbol esters in the oil separation of step 700, can be recovered (step 800), and used again for extraction in step 600. Thus, as fractions, a shell fraction I (usable eg as a fuel), a moist meal or meal phase II (usable eg as animal feed), an oil phase III (usable as a fuel) and possibly also a phorbol ester phase IV (usable in the pharmaceutical sector) are obtained , The economy of this process is particularly high. The use of alcohols as extractants in oils is considered to be unproblematic. Gas-tight, explosion-proof components can be used efficiently here. Residual contents of alcohol, even methanol is not critical, since these oils are mainly used for processing into biodiesel. For the production of biodiesel, methanol is added to the oil so that residual contents of methanol are not troublesome.

The extraction of phorbol esters by means of alcohol has already been carried out on a laboratory scale and is described e.g. in the context of this invention, it is merely an option for obtaining a phorbol ester-reduced oil for use in step 400.

In principle, however, step 400 can also be carried out with vegetable oil (rapeseed, soya, etc.).

In the following, aspects of variants of the invention will be described in more detail.

Trial 1:

800 g of Jatropha seed (wild sowing from Cape Verde) was broken manually with the help of pliers. The trays were separated manually. The refraction was done so that only a small amount of fines and dust was formed. Seeds, trays and pulp were analyzed: the seed contained 91% dry matter (TS), which consisted of 16% protein and 35.7% fat. The shell fraction of 298 g (37.7%) contained 91% TS, which consisted of 3.3% protein and 0.4% fat.

The core fraction of 502 g (62.3%) contained 91% TS, which was 24.6% protein and 56.5% fat.

Both fractions were optically pure, only with traces of the other fraction.

It turns out that manual peeling very effectively removes portions of the jatropha seed which have a relatively low fat content. Trial 2:

1 .013 kg of Jatropha seed (wild sowing from Cap Verden) were peeled by means of a test plant of the company Probat.

Breaking took place by means of reflex breakers with a gap of 3 mm. The brewery was operated at 1,300 rpm, the average throughput was 308 kg / h.

The separation of the shells was carried out in a pilot plant air classifier. The average throughput was 296 kg / h.

The following fractions were obtained:

1 . 507 kg core fraction (50%)

2. 494 kg shell fraction (48.8%)

3. 12 kg dust fraction from separator cyclone (1, 2%)

The shell fraction contained 91.4% TS, which consists of 7.3% protein and 7.8% fat.

The core fraction contained 91.2% TS, which consisted of 19.8% protein and 49.8% fat.

Both core and shell fraction optically still had shares of each other fraction.

It can be seen in this respect that even through automated peeling large amounts of jatropha seed are removed, which have only a relatively low fat content.

Trial 3:

300 g peeled, ground jatropha seed was mixed in a beaker with 450 g of water and stirred in a water bath at 90 ° C. for 60 minutes. This resulted in a pH of 6.2.

Another sample was adjusted to pH 3.0 with 90 ml of HCl and also stirred for 60 minutes in a water bath at 90 ° C.

Subsequently, the two samples were spun in a heated laboratory centrifuge for 3 minutes at 4,500 x g.

The solid was then analyzed for residual fat content.

While the sample without pH shift had a residual fat content of 12.06% (based on DM), the residual oil content of the oil-displaced sample with pH shift was only 3.6.

This proves the advantage of the pH shift. Trial 4:

160 kg of water were indirectly heated to 95 ° C. in a heatable stirred tank. Subsequently, 1 12 kg of peeled, ground Jatropha seed were entered. The suspension was adjusted to a pH of 3.0 with 5.8 kg of concentrated hydrochloric acid and the suspension was adjusted to a temperature of 90.degree.

The suspension was stirred gently in the container for 60 minutes.

Subsequently, the suspension was separated in the 2-phase separating decanter CA 220-08-33 (Westfalia Separator Group GmbH) into an oil phase and a phase of deoiled suspension. The drum speed was 4,750 rpm, the differential speed 18 rpm.

The feed rate was 300 l / h and was adjusted by means of a controllable progressing cavity pump.

The drainage capacity of the oil phase was 63 l / h.

The deoiled solid contained 34.8% TS, with 5.4% fat by dry weight.

Trial 5:

180 kg of already deoiled jatropha suspension with 34.8% DM and 5.4% fat (from test 4) in the dry substance were mixed in a stirred tank with 50 liters of water.

The suspension was stirred gently for 30 minutes, while heated to 90 ° C by indirect heat.

Subsequently, the suspension in the 2-phase Trenndekanter CA 220-08-33 (Westfalia Separator Group GmbH) was de-oiled in an oil phase and a phase

Suspension separately. The drum speed was 4,750 rpm, the differential speed 15 rpm.

The drainage capacity of the oil phase was 9 l / h.

The deoiled solid contained 29.6% DM, with 3.9% fat based on the dry matter.

The comparison of Experiments 4 and 5 shows the advantage of forming the oily suspension according to step c) of claim 1 and step d) of claim 1, in particular with a prior separation of the shell components (experiment 4). Trial 6:

36 kg of Jatropha oil thus obtained was mixed in a stirred tank with 1 liter of water and heated to 90 ° C with indirect heat.

Subsequently, the oil phase was separated in a solid bowl centrifuge BTC 3-03-107 (Westfalia Separator Group GmbH) in an oil and an aqueous phase. Solids present in the oil were collected in the centrifuge drum and removed after the trial.

The aqueous phase contained 2.0% TS and had a fat content of 0.05%. The oil phase had the following parameters:

Coke residue: 0.45% (m / m); Oxide ash: <0.005% (m / m); Phosphorus: <0.5 mg / kg; Sodium: <0.5 mg / kg; Magnesium: <0.5 mg / kg; Calcium: <0.5 mg / kg; Potassium: <0.5 mg / kg; Aluminum: <0.5 mg / kg; Iron: <0.5 mg / kg

Very important here is the very low phosphate and magnesium content of the oil phase.

After the experiment 4, an oil phase is first obtained by the process of claim 1. As described in claim 12, the yield can be improved by multiple de-oiling. This is very impressively confirmed by the optional desolventizations of experiments 4, 5, and 6. Experiment 7: (comparison of the end products of the compression, aqueous methods)

150 kg shelled, ground Jatropha seeds from experiment 2 (Cap Verden) were mixed with 190 kg of water in a stirred tank. By adding 9.5 kg of HCl (30%), a pH of pH = 3.0 was set.

The suspension was stirred for 1 hour at low speed and heated by steam (indirectly) to 90 ° C.

Subsequently, the suspension was separated in the 2-phase separating decanter CA 220-08-33 (Westfalia Separator Group GmbH) into an oil phase and a phase of deoiled suspension. The drum speed was 4,750 rpm, the differential speed 15 rpm.

The feed rate was 700 l / h and was adjusted by means of a controllable progressing cavity pump.

The deoiled solid contained 33.8% TS, with 19.9% fat by dry weight. The deoiled suspension was mixed with 50 kg of water, heated to 90.degree. C. in the stirred tank and a second time in the 2-phase separating decanter CA 220-08-33 (Westfalia Separator Group GmbH) separated into an oil phase and a phase of deoiled suspension.

The feed rate was 500 l / h and was set by means of an adjustable eccentric screw pump.

The deoiled solid contained 27.9% TS, with 14.1% fat by dry weight.

In parallel, a sample of unpeeled, ground Jatropha seed (Cap Verden) was processed in a laboratory screw press.

670 g of seed were in the auger press comet CA59G in press oil and

Processed press cake. The press was operated at a fixed speed and an outlet gap of 8 mm.

It contained 422.6 g of presscake and 247.4 g of press oil. The oil still contained 10% (v / v) sediment, which was removed in a laboratory centrifuge.

Subsequently, fine solids were removed from the oil by vacuum filtration in the laboratory filter (0.45 micron pore diameter).

Oil samples and presscake were analyzed and compared to the aqueous test.

Phase analysis Aqueous process screw press

reindeer

Seed TS (%, m / m) 96 96

Fat (%, on TS) 32.2 32.2

PE (%, on TS) 0.225 0.225

Protein (%, to 13.6 13.6

TS)

Oil PE (%, on TS) 0.504 0.625

Phosphorus 9.0 66.3

(Mg / kg)

Magnesium 3.0 17.1

(Mg / kg)

Bowls Fat (%, on TS) 7.3 -

Protein (%, to 7.3

TS)

PE (%, on TS) 0.06 - Shot fat (%, on TS) 14,1 5,8

Protein (%, to 46.1, 25.9

TS)

PE (%, on TS) 0.07 0.10

The content and magnesium of the oil obtained in the aqueous process was reduced to values below the detection limit by simple washing with water.

Experiment 8: (Extraction of PE by vegetable oil)

100 g in the aqueous process deoiled product with 35.0% DM and 4.9% residual oil content was mixed in a beaker with 10 g of rapeseed oil and heated to 90 ° C in a water bath.

The concentration of PE in the aqueous sample was determined to be 0.026%. This corresponds to a concentration of PE with respect to the oil before foreign oil addition of 0.53%.

The rapeseed oil was PE free.

After addition of the rapeseed oil, the PE concentration of the mixed oil is calculated to be 0.17%.

After reaching the temperature, the sample was separated by means of a laboratory centrifuge into an oil phase and an aqueous solid phase.

The heated laboratory centrifuge was operated at 90 ° C at 6,000 rpm. This corresponds to an average centrifugal acceleration of 4,500 x g. The samples were spun for 3 minutes.

The PE concentration in the oil thus obtained was 0.27%, the concentration in the deoiled solid decreased from 0.026% to 0.014%.

Experiment 9: (extraction of PE from jatropha oil by means of ethanol)

100 g of Jatropha oil were mixed with 200 g of ethanol and heated to 50 ° C in a water bath. To investigate the influence of the alcohol concentration, ethanol concentrations of 30-90% (m / m) were used. In order to prevent separation of the alcohol and oil, the mixture was mixed thoroughly by means of a magnetic stirrer.

After 10 minutes reaction time, the mixture was separated in a heated laboratory centrifuge into an oil and alcohol phase.

The heated laboratory centrifuge was operated at 50 ° C at 6,000 rpm. This corresponds to an average centrifugal acceleration of 4,500 x g. The samples were spun for 3 minutes.

The oil phase was carefully separated and examined for PE:

Concentration PE (%, on TS) PE reduction (%)

(Alcohol

% M / m)

Oil 0.304 0

0 0.275 9.54

30 0.299 1, 64

50 0.255 16.5

70 0.1 14 62.5

90 0.070 77.0

LIST OF REFERENCE NUMBERS

I mill

2 buffer tank

3 eccentric screw pump

4 mixing station

5 use containers

6 agitator

7 eccentric screw pump

8 decanters

9 buffer tank

10 eccentric screw pump

I I heat exchanger

12 centrifuge

Claims

1 . Process for the solvent-free fractionation of husked and minced jatropha seeds having a phorbol ester content which produces at least the following fractions:

a shot fraction (I) reduced in phorbol ester content relative to the phorbol ester content of the jatropha seeds;

a phorbol ester-containing jatropha oil (III),

with at least the following process steps:

200) adding water and acid to the minced jatropha seeds to form an oily suspension, the pH of the suspension being adjusted to <= 3.5;

300) depositing jatropha oil from the oily suspension, preferably in the centrifugal field to form the jatropha oil fraction and the shot fraction;

400) addition of phorbol ester-free or at least phorbol ester-reduced oil, in particular vegetable oil; to the shot fraction from step 300) and

500) separating extraction oil from the shot fraction from step 400), preferably in the centrifugal field.

2. Method for solvent-free fractionation of an unpeeled

Jatropha seed having a phorbol ester content which produces at least the following fractions:

a shell fraction (I)

a shot fraction (II) reduced in phorbol ester content relative to the phorbol ester content of the seed;

a phorbol ester-containing jatropha oil (III),

with at least the following process steps:

50) peeling the seeds to form the shell fraction and a husked jatropha seed fraction;

100) crushing the peeled jatropha seeds;

200) adding water and acid to the minced jatropha seeds from step 100) to form an oily suspension, the pH of the suspension being adjusted to <= 3.5; 300) depositing jatropha oil from the oily suspension preferably in the centrifugal field to form the jatropha oil fraction and the shot fraction;

3. The method according to claim 1 or 2, characterized in that in step 300) deposited Jatrophaöl - a crude oil - is oil polished.

4. The method of claim 1, 2 or 3, characterized in that the pH in step 200 is set to <= 3.2.

5. The method according to claim 4, characterized in that in step 200) acid and water are added.

6. The method according to claim 5, characterized in that in step 200) hydrochloric acid and water are added.

7. The method according to any one of the preceding claims, characterized in that after the addition of water and acid in step 200) before step 300), a residence time of at least 30 min, preferably 30-60 min, is maintained (step 250).

8. The method according to any one of the preceding claims, characterized in that in the steps 300) and / or 500) processing takes place in a decanter, which generates the required centrifugal field.

9. The method according to any one of the preceding claims, characterized

characterized in that the oil-containing suspension of step 400) has a temperature of 60-80 ° C before the deposition of the oil phase.

10. The method according to claim 9, characterized in that the oil-containing suspension of step 400) before depositing the oil phase has a temperature of 80-95 ° C.

1 1. Method according to one of the preceding claims, characterized in that in step 300), a water-to-product ratio in the range of 1 + 2 to 2 + 1 is set.

12. The method according to any one of the preceding claims, characterized

characterized in that the water content of the suspension in step 200) is greater than 35% by weight, preferably greater than 40% by weight, based on the total mass of the suspension.

13. The method according to any one of the preceding claims, characterized in that prior to crushing the plant seeds in step 200, a cleaning of the Jatrophasamen.

14. The method according to any one of the preceding claims, characterized in that in step 400 vegetable oil is added.

15. The method according to any one of the preceding claims, wherein in step 400) vegetable oil in the ratio between 1 + 10 to 1 + 1 - 1. Value: vegetable oil; 2: value residual oil content in shot fraction - is used.

16. The method of claim 15, wherein in step 400) vegetable oil in the ratio 1 + 2 is used.

17. The method according to any one of the preceding claims, characterized in that in step 400 jatropha oil is used, from which the phorbol esters were previously separated.

18. The method according to any one of the preceding claims, wherein in step 400) as a vegetable oil reduced in phorbol ester, in particular phorbol ester free Jatrophaöl in the ratio 1 + 2 is used.

19. The method according to any one of the preceding claims, wherein in step 400) as a vegetable oil reduced in phorbol ester, in particular phorbol ester free Jatrophaöl in the ratio 1 + 2 is used.

20. The method according to any one of the preceding claims, characterized in that after the optional cleaning and before the crushing of the plant seeds or nuts drying of the plant seeds or nuts takes place.

21. Method according to one of the preceding claims, characterized in that the deposition of the oil phase is carried out by a multiple de-oiling of the suspension.

22. The method according to any one of the preceding claims, characterized

characterized in that the phorbol ester is obtained as a concentrate

23. A method for reducing the phorbol ester content of a preferably de-oiled jatropha seed meal with the following method steps:

400) addition of phorbol ester-free or at least phorbol ester-reduced oil, in particular vegetable oil; to the shot and 500) separating extraction oil from the shot fraction from step 400), especially in the centrifugal field to obtain the phorbolestergahalt-reduced shot fraction.

24. The method according to claim 23, characterized in that the steps 400) and 500) are repeated several times.